Catalytic compositions for butadiene polymerization and processes using said compositions



United States Patent 3,468,867 CATALYTIC CUMPOSITIONS FOR BUTADIENE PDLYMERIZATION AND PROCESSES USING SAllD COMPOSITIONS Walter Marconi, Alessandro Mazzei, and Gabriele Lugli, San Donato Milanese, Milan, Italy, assignors to SNAM S.p.A., Milan, Italy, a company of Italy No Drawing. Continuation of application Ser. No. 494,874, Oct. 11, 1965. This application Nov. 8, 1968, Ser. No. 774,549 Claims priority, application Italy, Feb. 3, 1965, 887/65 The portion of the term of the patent subequent to Sept. 16, 1986, has been disclaimed Int. Cl. (308d 1/14, 3/08 US. Cl. 260-943 5 Claims ABSTRACT OF THE DISCLOSURE For polymerizing butadiene to produce polymers of essentially 1,4 cis structure, a linear polymeric compound of aluminum of polyirninic nature is used having repeating units of the type:

This is a continuation of Ser. No. 494,874, filed Oct. 11, 1965, now abandoned.

The present invention relates to new catalytic compositions and to butadiene polymerization processes using said compositions.

Diene polymerization is generally known from Belgian Patent No. 551,851 using catalytic systems comprising organo-metallic compounds together with compounds of transition metals. In the case of butadiene such systems can yield a polymer having a high content of 1,4 cis units.

Catalyst compositions are also provided in said patent containing hydride compounds together with compounds of transition metals capable, in the case of butadiene, of yielding structures having 1,2 or 1,4 trans linkages, depending on the used transition metal. Accordingly, the use of TiCl, together with hydrides yields 1,2 structures, While the use of Til, in place of TiCl, yields 1,4 trans structures. The latter structure can also be obtained according to another Phillips patent (US. Patent 3,066,129) using Ticl together with I The state of the art is sufficiently illustrated in Linear and Stereoregular Addition Polymers published by Interscience, 1959, page 138, lines 7 to 18.

We have now found that it is possible to obtain 1,4 cis polybutadiene using a linear polymeric compound of aluminum of polyiminic nature, containing in its molecule repeating units of the type --Al--N a it where R is an aryl, alkyl or cycloalkyl hydrocarbon radical.

3,468,867 Patented Sept. 23, 1969 11R--NH1.HCl nLiAlHl where R and R, identical or different, are groups selected from aryl, alkyl or cycloalkyl hydrocarbon radicals such as, for example, CH C H nC H, C H and the like.

Said compounds will also be called in the course of this specification as aluminum iminic polymers.

The preparation of said compounds is described by E. Wilberg, A. May in Z. fiir Naturforsch. 106, 232 (1955) and more particularly by R. Ehrlich and coll. in Inorg. Chem. 3, 628 (1964). Molecular Weight measurements show them to be polymers in which n is 4.

When n is small (from 4 to about 50), such compounds are soluble in aromatic solvents and sometimes also aliphatic solvents. Higher molecular weight compounds are insoluble in common solvents, although they are still efiicient catalysts in the presence of TiCl for example, since they still contain an equivalent of active hydrogen for each aluminum atom. Such compounds have the advantage, especially with respect to the alkyl aluminum compounds used conventionally of greater stability towards oxidizing and hydrolizing agents and of greater safety in handling. Together with said aluminum iminic polymers, transition metal compounds are used selected from: titanium trichloride, titanium tetrachloride, titanium tetraiodide, vanadium trichloride, vanadium tetrachloride, nickel chloride, vanadium oxychloride, cobalt chloride, cobalt acetylacetonate and the like.

According to the present invention, together with the previously defined irninic aluminum polymer and with the transition metal compound also a third component is normally used which is an aluminum halide selected from aluminium iodide, chloride or bromide.

The selection of the aluminum halide is a function of the particular transition metal compound being used in the polymerization process, so, for example, in the case of cobalt compounds either aluminum chloride or bromide or iodide can be used, aluminum chloride being though the preferred one; in the cae of titanium compounds, on the other hand, if they contain iodide ions any aluminum halide can be used or it can also be absent, in which case the catalytic composition of the present invention will consist of a binary composition comprising only the aluminum iminic polymer and the titanium compound.

If, on the other hand, iodine is absent in the latter, as is the case of the other titanium halides or, for example, of the alkoxy compounds having the formula Ti(OR) (where R is a hydrocarbon radical), the aluminum halide to be used is the iodide one or a mixture of aluminum halides comprising the iodide.

The operative conditions for the use of the catalytic compositions of the present invention in the case of butadiene polymerization to a substantially 1,4 cis poly- 3 4 mer, comprise temperatures ranging from 30 to bath at the desired temperature and for the desired time. +l C. and pressures from atmospheric to 20 atm. At the end, the bottles were opened and their content Solvents which can be used are of hydrocarbon nature poured in methyl alcohol containing an antioxidizer. The and comprise aliphatic, aromatic and cycloaliphatic hydrocoagulated solid polymer was kept in an oven under carbons. vacuum at 45 C. until constant weight was reached. On Examples of preferred solvents are benzene, toluene, the dry polymer the yield was calculated and infrared n-heptane, n-o t th i i o r d i tu th f, analysis and the measurement of intrinsic viscosity in toluene at 30 C. were made. EXAMPLES 1 3 The polymerization conditions and the obtained results 5 g. of LiAlH (0.132 mole) and 130 cm. of anare shown in Table 1.

TABLE 1* H c 115 l Solid AI=N in Polymer- Polymer ization Polymeryield, IR Analysis, Percent Run SolutionA Atomic Ratio Temperaization Gram Number (cmfi) H (active)/Ti ture, C. Time, Hr. Percent 1,4 cis 1,4 trans 1,2

*TiCl 2.275 lmnoles; A113, 2.275 mmoles; toluene, 100 cm}; butadiene, g.

hydrous benzene are charged to a two neck flask provided EXA 4 5 with a reflux condenser. To the stirred suspension 9.45 g. of ethylamine hydrochloride (0.166 mole) are added Butadiene was polymerized with a catalytic system over a period of about minutes at room temperature. made up by the aluminum iminic polymer (the previously The mixture is p at for 16 houfs at room described solution A) and by TiI Cl having two diftemperature for further hours. The mixture is filtered ferent ratios H (active) /Ti.

under nitrogen and a solution is obtained which when analysed gave the following results:

A1=2.25 g./l00 cm. N=1.35 g./100 cmfi; Cl=0.l0

The polymerization procedures were the same as those described in the previous examples; the used quantities and g n00 cm obtained results are shown in Table 2.

TABLE 2* H; 0 11 I: l 1 Solid Al=N n p ym r Polym. Polym. yield, IR Analysis, percent Example Solution A TiIzClg, Atomic ratio temp., time, gram Number (emfi) mmoles H (aetive)/Ti 0. Hr. percent 1,4 cis 1,4 trans .3

Toluene, 100 cmfi; butadiene, 15 g.

H (active)=1620 cm. 100 cm. which correspond EXAMPLE 6-7 Wlth good approxlmanon to the empmcal formula: Butadiene was polymerized with a three components H 021151 catalytic system made up by the previously described solu- A1=NC2H5 tion A compound, cobalt diacetylacetonate, and AlBr L 0 Operating procedures were similar to those previously Such solution winbecalled 1 i described, i.e. 100 cm. of toluene, the desired quan- We have carried out butadiene polymerization runs y 0f 501110011 the desired q y of AlBrs with the catalyst obtained mixing in convenient ratios toluene solution, butadiene and finally the toluenic solusolution A with a toluenic solution of TiCl and a tolut1011 0f 2( Y t ne) Were introduced 111 enic solution of A113. The polymerization runs were carsuccession into the reaction vessel. The used quantities, ried out in drinking bottles of 200 cm. capacity, intropolymerization conditions and obtained results are shown ducing in succession 100 cm. of anhydrous toluene, the in Table 3.

TABLE 3* Solid Atomic Molar polymer IR Analysis, percent Ratio Ratio yield,

Example Solution A, 00112, H (active)! AlBl'g/ gram 1, 2 AlBri, Number em. nimoles C0 CoAi percent 1,4cis 1,4traiis percent mnioles Tolugne, 100 0111. butadiene, 15 g.; polymerization temperature, +2 0.; polymerization time, 5 hours; CoAz=cobalt acetylace ona c.

desired quantity of solution A, 2.29 cm? of a 0.105 molar EXAMPLE 8 toluenic solution of A11 The bottle was closed with a neoprene plug and a bored crown cap through which 15 g. of butadiene were introduced, using a hypodermic needle Wfilded to the butadiene cylinder- The aluminum iminic o1 'mer is re ared b react y} CHI-3 of a 0-2275 molar Tlcl tohfemc ing in a two neck flask, PI 'ZWi dCd with a r efiux coirdenser on s introduced y means of a hypodermlc Syringe, and a stirrer, 8.2 g. of LiAlH 0.215 mole) in :00 under stirring. cm. of anhydrous toluene and 17.7 g. (0.195 mole) of The bottles were kept inside a rotating thermostatic n-butylamine hydrochloride. The mixture is stirred at Butadiene was polymerized with a three component catalytic system made up by the n-butyl-iminic polymer. cobalt diacetyl-acetonate and aluminum bromide.

50 C. for 3 hours and then at room temperature for 70 hours.

The mixture is filtered and the limpid solution is concentrated under vacuum to about two-thirds if its initial volume. This solution is analyzed: A1=2.58 g./100 cm. of solution; N=l.40 g./100 cm. H(active)=2558 cm. 100 cmfi; Cl=absent.

The analysis corresponds, with good approximation, to an empirical formula P l "win-1:1 --A1=Nn. C 4110 Such solution is referred to as solution B.

The butadiene polymerization recipe is as follows:

Toluene-100 cmfi.

Solution B-1.85 cm. (corresponding to l.77 l()- g.-

atom of aluminum.

AlBr-1.47 mmoles.

CoA 0.0059 mmole.

Butadiene16 g.

The atomic ratio H(active)/Co is 300 and the molar ratio AlBr /CoA is 250.

The operating procedures were similar to the ones described in Examples 6 and 7.

Polymerization was carried out at +2 C. for 60 hours.

10.6 g. of dry polymer were obtained (yield=66%), which showed the following composition at IR analysis: 94.5% 1,4 cis; 2.5% 1,4 trans; 3% 1,2.

EXAMPLE 9 Aluminum phenyl iminic polymer was synthesized in a 500 cm. capacity two neck flask provided with a reflux condenser and a stirrer by reacting: 7.1 g. of LiA1H (0.187 mole) in 170 cm. of toluene with 13.1 g. of aniline hydrochloride (0.168 mole). The reaction was carried out under stirring for 75 hours at room temperature and eventually heating to 50 C. for 8 hours. The mixture was filtered under nitrogen and the limpid solution was concentrated under vacuum to about 20% of its initial volume.

Analyses were carried out on the limpid solution. The results were: A1=0.719 g./100 cm. of solution,

gram atoms N gram atoms Al Cl=absent which corresponds, with approximation, to a formula of the following type:

nd gram atoms H (active) =12 gram atoms Al L that Such solution is referred to as solution C.

Butadiene was polymerized with a catalytic system made up by TiC1 AlI and solution C with established ratios between the components.

The recipe is:

The operating procedures were as those described in Example 1.

Polymerization was carried out at C. during 2 hours.

6 18.5 g. of dry polymer were obtained with a yield of 92%.

1R analysis gave the following composition: 91.5% 1.4 cis; 3.5% 1,4 trans; 5% 1,2.

EXAMPLE 10 Butadiene was polymerized with a catalytic system made up from the compound of the previously described solution C and T il Cl The recipe is as follows:

Toluene-100 cm.

Solution C1.83 cm. (corresponding to 0.488 milliatom Al).

TiI Cl 0.162 millimole.

Butadiene20 g.

Polymerization temperature-5 C.

Polymerization time-2.5 hours.

The results of the run are: solid dry polymer 17.8 g. corresponding to a yield of 88%; IR analysis of polymers: 94% 1,4 cis;2% 1,4 trans; 4% 1,2.

We claim:

1. A process for polymerizing butadiene to substantially 1,4 cis polybutadiene comprising contacting butadiene with a catalyst system obtained by combining:

a compound of a transition metal selected from the group consisting of titanium trichloride, titanium tetrachloride, vanadium tetrachloride, nickel chloride, vanadium oxychloride, cobalt chloride and cobalt acetylacetonate and a polyiminoalane represented by the formula:

wherein R is an alkyl, aryl, or cycloalkyl radical and n.

is from 4 to about 50 in an aromatic hydrocarbon solvent and carrying out the polymerization reaction at temperatures between 30 and +100 C. and at pressures between 1 and 50 atm. so that a polymer is obtained having a content of more than of 1,4 cis units.

2. A process according to claim 1 wherein the transition metal compound is a titanium halide containing iodine.

3. A process according to claim 1' wherein the transition metal is a titanium halide chosen among TiCl, and TiBr and the catalyst system includes a third component selected from the group consisting of iodine and inorganic iodides.

4. A process according to claim 1 wherein the transition metal compound is a cobalt compound and the catalyst system includes a third component selected from the group consisting of aluminum chloride, aluminum bromide and aluminum iodide.

5. A catalytic composition comprising the reaction product of a compound of a transition metal selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, vanadium trichloride, zirconium tetrachloride, cobalt chloride, cobalt acetylacetonate, manganese chloride and nickel chloride with a polyiminoalane represented by the formula:

R is an alkyl, aryl or cycloalkyl radical and n is from 4 to about 50.

(References on following page) 7 8 References Cited JAMES A. SEIDLECK, Primary Exammer UNITED STATES PATENTS R. A. GAITHER, Assistant Examiner 3,163,611 12/1964 Anderson et a1 252-429 3,178,402 4/1965 Smith et a1. 260--94.2

3,255,169 6/1966 Kearby 260-93.7 5 252431, 438, 429, 428; 26094.6 

